US3840373A

US3840373A - Green sensitive silver halide photographic emulsion

Info

Publication number: US3840373A
Application number: US00203541A
Authority: US
Inventors: Y Oishi; Y Yoshida; K Shiba; M Hinata
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1970-12-01
Filing date: 1971-12-01
Publication date: 1974-10-08
Anticipated expiration: 1991-10-08
Also published as: JPS494650B1; CA987528A; FR2117178A5; DE2159615A1; BE776109A

Abstract

A silver halide photographic sensitive material having a green sensitive layer and suitable for use in the diffusion transfer method is disclosed.

Description

United States Patent [191 Shiba et al.

[111 3,840,373 [451 Oct.8, 1974 GREEN SENSITIVE SILVER HALIDE PHOTOGRAPHIC EMULSION Inventors: Keisuke Shiba; Masanao Hinata;

Yasushi Oishi;'Y0shinobu Yoshida, all of Kanagawa, Japan Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan Filed: Dec. 1, 1971 Appl. No.: 203,541

Foreign Application Priority Data Dec. 1, 1970 Japan 45-106113 US. Cl 96/77, 96/99, 96/124 Int. Cl. G03c l/40, G03c l/lO, G03c 1/14 Field of Search 96/124, 77, 3, 29 D, 99,

References Cited UNITED STATES PATENTS 2,973,264 2/1961 Nys et a1 96/124 2,983,606 5/1961 Rogers 96/29 D 3,173,791 3/1965 Kalenda 96/137 3,397,060 8/1968 Schwan et al.. 96/124 3,415,646 12/1968 Land 96/29 D 3,663,210 5/1972 Sato et a1 96/124 Primary ExaminerDavid Klein Assistant ExaminerRichard L. Shilling Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [5 7] ABSTRACT A silver halide photographic sensitive material having I a green sensitive layer and suitable for use in the'diffusion transfer method is disclosed.

8 Claims, 2 Drawing Figures GREEN SENSITIVE SILVER HALIDE PHOTOGRAPI-IIC EMULSION BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a photographic sensitive material which contains dye developers suitable for the diffusion transfer method and which is spectrosensitized. The invention relatesmore particularly to a green sensitized sensitive material.

2. Description of the Prior Art Compounds containing a moiety having a dyeing function and a moiety having a development function for silver halide in the same molecule are necessary among photographic elements for forming color images according to the diffusion transfer process. Such compounds are known in general as dye developers.

It has been reported in U.S. Pat. No. 2,983,606, British Pat. No. 804,971 and French Pat. No. 1,313,767 that when a sensitive element containing a dye developer and silver halide is exposed to light and treated with an alkalaine treatment composition, development proceeds in the exposed area, the dye developer is changed so as not to diffuse substantially whereas the developer may diffuse in the unexposed area, and the element is contacted to an image-receivng element to yield a dye transfer image resulting in a positive image in which the density of the image is adversely proportional to the amount of exposure.

The dye developers to be used in this invention are described in the literature. The dye developers may not diffuse substantially in a colloid layer such as a hydrophilic organic colloid which is used at a neutral pH- value in a photographic emulsion but diffuse in such emulsion in the presence of alkaline treatment solution. Available dye developers are described in many patent specifications, for example, Australia Pat. No. 220,279; German Pat. No. 1,036,640; British Pat. Nos. 804,971; 804,973, 804,974 and 804,975; Belgian Pat. No. 554,935; French Pat. Nos. 1,168,292 and 1,313,765; Canadian Pat. Nos. 577,021 and 579,038; and US. Pat. Nos. 3,320,063, 3,255,001, 2,992,106, 3,297,441,

In general, as mentioned above, the dye developer is a compound which contains the dyeing moiety and at least one silver halide developing group in the same molecule. The term silver halide developing group means a group which is suitable for the development of exposed silver halide, The preferred'silver halide developing group is the hydroquinonyl group. The developing group may also be o-dihydroxyphenyl or oand pamino-substituted hydroxyphenyl groups. In general. the developing group contains a benzenoid developing group, i.e., aromatic developing group which forms a quinonoid, i.e., a quinone substance in the oxidation. The dyeing moiety of typically available dye developers is the azo or anthraquinone dyeing moiety. in the dc scription of this invention, the dye developers having the azo dyeing moiety are referred to as the azo developers and those having the anthraquinone dyeing moi-.

ety as anthraquinone dye developers.

As is well known in the field, dye developers represented by azo or anthraquinone dye developers reduce the sensitivity of silver halidephotographic emulsions and especially the spectrosensitized silver halide emulsions (in this case, the absorption due to the dye developer is subtracted). The reduction of sensitivity due to the dye developer is observed not only in the direct addition of the dye developer to the green spectrosensitized silver halide emulsion but in the indirect addition of the dye developer to the green sensitive emulsion layer, i.e., in the contact of the dye developer layer to said sensitive layer. In the latter case, a part of the'dye developer in the dye developer layer may diffuse into the sensitive layer;

3. Objects of the Invention Y Accordingly, an object of this invention is to provide a green sensitive layer for a'silver halide photographic sensitive material'having a high green sensitivity in the presence of a dye developer. More particularly, an object of this invention is to provide a silver halide photographic sensitive material having a green sensitive layer and being suitable for the diffusion transfer method. 7

Otherobjects of the invention will be apparent to those skilled in theart as the description of the invention proceeds.

BRIEF DESCRIPTION OF THE DRAWINGS wherein R representshydrogen atom or lower alkyl (C,.;,) such as methyl, ethyl, etc.

Y, and Y, each represent a hydrogen atom, loweralkyl such as methyl, ethyl, etc., halogen atomsuch as chlorine and bromine, hydroxyl, alkoxy such as methoxy, ethoxy, etc., amino group such as aminoigroup, methyl amino group, etc., acylamido group such as acetamido group, etc., alcyloxyl group such as acetoxyl group, etc., carbalkoxy group such as carbethoxy group, etc., and alkoxycarbonylamino group such as ethoxycarbonylamino group.

Y and Y each represent a hydrogen atom, lower alkyl such as methyl, ethyl, etc., halogen atom such as chlorine, bromine and fluorine, hydroxyl group, alkoxy such as methoxy, ethoxy, etc., amino group such as amino group, methyl amino group, etc., acylamido group such as acetamido group, etc., acyloxyl group such as acetoxyl group, etc., carbalkoxy group such as carbethoxy group, etc., alkoxycarbonylamino group such as ethoxycarbonylamino group, etc., and phenyl radical.

Y and Y each represent a hydrogen atom or the atomic grouping necessary for the formation of a benzene ring through the connection of Y;, with Y or of Y, with Y Y and Y each can be connected with Y, or Y, respectively to form a benzene ring excepting, of course, that both Y with Y and Y with Y form at the same time a benzene ring or both Y with Y and Y, with Y form at the same time a benzene ring.

R, and R each represent an alkyl group such as methyl, ethyl, n-propyl, etc., substituted alkyl radical, which is used in general for cyanine dyes, such as hydroxyalkyl (for example, 2-hydroxyethyl, 4- hydroxybutyl, etc.), acetoxyalkyl '(for' example, 2- a'cetoxyethyl, 3-acetoxypropyl, etc.), alkoxyalkyl (for example, 2-methoxyethyl, 4-butoxybutyl, etc.), alkyl radical containing carboxyl group (for example, 2- carboxyethyl, 3-carboxypropyl, Z-(Zcarboxyethoxy)ethyl, etc.), alkyl radical containing sulfo group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4- sulfobutyl, 2-hydroxy- 1 -sulfopropyl, 2-( 3-sulfopropoxy)ethyl, Z-acetoxy-l-sulfopropyl, 3-methoxy-2-(3- sulfopropoxy)propyl, 2-(2-(3-sulfopropoxy)ethoxy)ethyl, 2-hydroxy-3-(3'-sulfopropoxy)-propyl, etc.), aralkyl (for example, benzyl, phenylethyl, psulfobenzyl, p-carboxybenzyl, p-sulfophenethyl or allyl radical), and at least one of R, and R is an alkyl radical containing a carboxyl or sulfo group.

X represents an anion such as chloride, bromide, iodide, thiocyanate, sulfonate, perchlorate, p-toluenesulfonate, methylsulfonate, ethylsulfate, etc., and n represents l or 2, wherein n 1 when said dye forms an intr'amolecular salt.

wherein R represents a lower alkyl such as methyl, ethyl, etc. or allyl radical.

Y, represents a hydrogen atom or halogen atom such as chlorine, bromine or fluorine.

Y, represents a hydrogen atom, a halogen atom such as chlorine, bromine and fluorine, etc., alkoxy group such as methoxy, ethoxy, etc., amino group such as amino, methyl amino, etc., acylamido group such as acetamido, etc., acyloxyl group such as acetoxyl, etc., al-- koxycarbonylamino groupsuch as ethoxycarbonylamino, etc.

Y represents a hydrogen atom, lower alkyl radical such as methyl, ethyl, etc., halogen atom such as chlorine and bromine, hydroxyl and alkoxy group such as methoxy, ethoxy, etc.

Y represents a hydrogen atom, lower alkyl radical such as methyl, ethyl, etc., halogen atom such as chlorine, bromine and fluorine atom, alkoxy group such as wherein R, and R each represents alkyl radical such as methyl, ethyl, propyl, butyl, etc.; Y and Y each represents hydrogen atom or halogen atom such as chlorine, bromine, iodine andfluorine; Y Y each represents hydrogen atom, halogen atom such 'as chlorine, bromine, iodine and fluorine ator n, alkoxy group such asmethoxy, ethoxy, butoxy, etc., amino grop such as amino, methyl amino,'dimethyl amino, etc., acylamido Yrs (III) group such as acetamido, etc., alcyloxyl group such as acetoxy, etc., alkoxycarbonylamino' group such as ethoxycarbonylamino, etc., cyano group, trifluoromethyl group, alkylsulfonyl group such as methylsulfonyl, etc., sulfamylv group, alkylaminosulfonyl group such as ethylaminosulfonyl, diethylaminosulfonyl, etc.,

morpholinosulfonyl group and piperidinosulfonyl group; and R R X and n have the same meanings as given in formula (I). r

The sensitizing dyes to be used in this invention are known. Dyes represented by the general formula (1) and (III) are the sensitizing dyes described in French Pat. No. 1,108,778 (Sept. 14, 1955), U.S. Pat. No. 2,503,776, US. Pat. No. 2,912,329 (Nov. 10, 1959) and US. Pat. No. 3,397,060 (Aug. 13, 1968) and can be synthesized readily for those skilled in the art with reference to those patent specifications, and those not described in said patent specifications can also be synthesized readily according to similar methods thereto.

The dyes represented by the general formula (II) are the sensitizing dyes described in the Japanese Publication 14030/69 (Jan. 18, 1966) and can be synthesized readily for those skilled in the art in reference to the publication specification, and those not described in the specification can be synthesized readily according to the similar method thereto. The following material is exemplary of methods of preparation of the dyes represented by the general formula (ll). i

- The sensitizing dyes used in the present invention may be-prepared by the condensation methods known to those skilled in the art. That is, the unsymmetric carbocyanine dye used in the present invention may be obtained by condensing an acetanilide intermediate compound with a cyclic quaternary ammonium salt having an active methyl group in a solvent such as nitrobe nzene, an alcohol or acetic anhydride in the presence of a suitable organic base such as triethylamine or piperidine. In the case of employing an anilino intermediate 1 then subjecting thus formed acetanilide intermediate compound in situ to the subsequent condensation reaction.

( 1193 03 (CH2)3S OQNa in one method for the formation of a color transfer image by using color developers, at least two selectively sensitized sensitive layers are placed in contact on a support and treated at the same time and without being separated together with a single common imagereceiving layer.

FIG. 1 illustrates one embodiment of a method for the formation of monochromic transfer image. The sensitive element consists of a support 11, a layer containing a color image-forming component 12 and a silver halide emulsion layer 13. Further, a vessel 16 capable of being ruptured and carrying an alkali treating composition is placed on the sensitive element, which is shown apart from the treating composition. On the other hand, an image-receiving element consists of a support 15 and an image-receiving layer 14. After exposure, the image-receiving element is in contact with the sensitive element and the vessel 16 capable of being ruptured is ruptured by applying a suitable pressure,

e.g., by progressing between a pair of opposed and suitably grooved rolls (not shown) tospread the liquid treating composition layer-like between said elements. The treating composition penetrates into the silver halide emulsion and develops the latent image contained in the emulsion. The color image-providing component migrates from the unexposed area to the contacted image-receiving element to form a positive color image resulting from the exposure thereon. After at least a part of the color image-forming element is then transferred, the image-receiving element is removed from the contact with the sensitive element.

The silver. halide emulsion layer consists of, for example, a blue sensitive silver halide emulsion layer and a green sensitive silver halide emulsion layer, each of said emulsions containing a magenta dye developer and a cyan dye developer respectively. The dye developer can be incorporated in the silver halide emulsion layer (for example, in the form of particles) or contained in a suitable layer below the silver halide emulsion layer. Each combination of the silver halide emulsion layer and the dye developer layer is separated from the other combinations through a suitable intermediate laye e.g., a gelatin or polyvinyl alcohol layer.

The natural color sensitive material of this type consists of a support carrying a red sensitive silver halide emulsion layer, a green sensitive silver halide emulsion layer and a blue sensitive silver halide emulsion layer, each of said emulsions containing a cyan dye developer, a magenta dye developer and a yellow dye developer. The manner of containing said dye developers is the same as mentioned above;

In a further method for the formation of a multi-color image, a plurality of sensitive elements suitable for the treatment with more than one treating liquid composition in connection to a suitable number of imagereceiving layers and suitable dye developers are contained for example in the sensitive elements.Examples of the film-constitution of this type are described in U.S. Pat. No. 2,647,049. 1

In a still further method for the formation of a multicolor image, sensitive silver halide emulsion layers comprising at least two selectively sensitized sensitive micro-elements which are disposed in the form of a sensitive screen are used. For example, each of the sensitive micro-elements contains a suitable dye developer in the silver halide emulsion layer or in the other emulsion layer. For example, the sensitive-silver halide layer consists of a sensitive screen of a blus sensitized emulsion micro-element and a green sensitized emulsion mi- N l 2 cro-element, each of said elements being in contact with each other in the screen pattern and containing a magenta and cyan dye developer respectively. Sensitive A dye developer which provides cyan, magenta or yellow to the green'sensitive emulsionto be used in this invention is .used and further dye developers of other colors such as black dye developers as well as a mixture of dye developers may be used.

The dye developer to be used in this invention may be introduced into thesensitive element, e.g., each silver halide emulsion, or into .the upper or lower layer thereof. The layer of such dye developer may be obtained by coating a solution containing about 0.5 8 percent by weight of a dye developer dispersed in a col-. loidal binder such as gelatin or dissolved in a synthetic polymer binder such as cellulose hydrogenacetate phthalate. 1

The alkali treating composition to'be used in this invention is an aqueous solution of at least one'alkali'ne compound such as diethyl amine, sodium or potassium hydroxide 'or sodium carbonate. When the alkali treating composition is applied by spreading, preferably as a relatively thin uniform layer, the composition-can substantially affected by standing for a longtime in the.

solution. An alkali treating composition containing mordant can be used also, which is known for example from Japanese Publication No. 6449/63. Examples of suitable alkali treating compositions are described in the examples of the text of this invention. Occasionally, it is desirable to apply the alkali treating composition to the sensitive element prior to the exposure according to the procedure described in U.S. Pat. No. 3,087,816.

The alkali treating-composition may contain auxiliary developers, i.e., a development accelerator (s) such as p-methylaminophenol, 2,4-d-iaminophenol, pbenzylaminophenol, hydroquinone, toluhydroquinone, phenyl hydroquinone, 4-methylphenyl hydroquinone and others. As described in U.S. Pat. No. .3,039,869,-a plurality of auxiliary developers 'such'asthe combination of 3-pyrazolidone and benzenoid developer can be used. As-examples of thefcombination of auxiliary .developers, there are mentioned a couple of l-phenyl-3- pyrazolidone and p-benzylaminophenyl as well as of l-phenyl-3 -pyrazolidone and 2,.5-bisethylaminohydroquinone..These auxiliary developers are used in the alkalitreating composition or at least a part thereof may be contained previously in the silver halide emulsion layer or a layer containing a dye developer. The oxidation-reduction reaction is repeated in thedye developer-auxiliary developer-exposed silver halide-system, in which the auxiliary developer serves a catalytic function. i

opers are described in Japanese Pat. Publication 392/65 and contain carboxyalkyl or sulfoalkyl group (the alkylene, chain used is n-alkylene). In particular, for the use of anthraquinone dye developers, a sufficient sensitization cannot be obtained without a large amount of sensitizing dye per unit of silver halide because the dye developer is apt to desorb the sensitizing dye from the silver halide. However, when a multi-layer material is prepared with a large amount of sensitizing V dye, the sensitizing dye in the green sensitive emulsion layer diffuses disadvantageously into other silver halide sensitive layers (e.g., blue or red sensitive layers), which is accordingly spectrosensitized. In particular, a sensitizing dye having an alkyl radical containing a carboxyl or sulfo group is apt to diffuse and spectrosensitize other silver halide layers. However, the combined use of sensitizing dyes to be used in this invention surprisingly provides a highly green sensitive emulsion layer with a strikingly reduced sensitization of the other layers.

On the other hand, it has been revealed in, for example, US. Pat. No. 2,913,329 that the combination of sensitizing dyes to be used'in this invention provides a good result in the presence of a dispersion of color couplers. As shown in Example 3, however, it has been found that the combination of sensitizing dyes provides an unexpectedly great effect when the dye developers according to this invention are compared with the use of the coupler dispersion.

In the combined use of sensitizing dye and dye developer, the interaction of said sensitizing dye and said dye developer (the mechanism of said interaction is not explained theoretically and may be perhaps the desensitization effect due to the dye developer) results in a remarkably reduced sensitivity of a green emulsion. However 'the use of combination of specified sensitizing dyes to be used in this invention can lower said interaction to provide a highly green sensitive emulsion.

The use ratio of sensitizing dye represented by the general formula (I), (II) and (III), i.e., the ratio of sensitizing dye of the formula (I) to'that of formula (II), the ratio of desensitizing dye of the formula (I) to that of formula (III) or the ratio, of sensitizing dye of the formula (II) to that of formula (III) is not especially critical. However, it is especially effectively within. the range of 9-1 1-9 by weight and may be varied accord ing to the purpose of use.

The method for adding the sensitizing dye to the photographic emulsion is well known in the field for manufacturing a photographic emulsion. In general, it may be mixed as a solution in a solvent such as water, methanol, ethanol, methyl cellosolve and the like or added to the photographic emulsion. In this case, for thedissolution, a supersonic vibration may be used. The amount of sensitizing dye used may be varied according to the nature of each silver halide emulsion, the desired result, etc. In general for the optimum sensitization, 0.005 0.3 g of dye per g of silver halide is sufficient.

As silver haldide emulsions to be used in this invention, there may be used silver halides such as silver chloride, bromide, iodobromide, chlorobromide and chloroiodobromide, and silver iodobromide.

While a conventional gelatin-silver halide emulsion is used in this invention, resinous materials which show no harm to the sensitive material or cellulose derivatives may be used instead of a part or all of the gelatin.

hardeners, coating assistants, plasticizers, development accelerators, air anti-foggants and the like, and may be coated in a common manner on a suitable supporter, e.g., glass, film of cellulose derivative, synthetic resin fifth, synthetic paper, Baryta paper, photographic paper coated with polyolefin film and the like.

a The image-receiving element to be used-in this inven- 3,003,872; 3,043,689; 3,065,074; 3,148,061; 3,239,337; 3,353,956; and 3,362,819, I

In some cases, the dyeable layer comprises analkali treating composition which is suitable to remain adhered to'the support on stripping. 3

The support of said image-receiving element is p'ref-.

erably synthetic paper, papers such as Barytapaper, photographic paper coated'with'a polyolefin film, and glass, films of cellulose derivative and synthetic resin may be used. v

This invention will be more fully illustrated by the following examples which are not intended to restrict the scope of this invention.

EXAMPLE 1 3g of magenta dye developer 4-isopropoxy-2-(p-(l3- hydroquinonyl-ethyl)-phenylazo) l-naphthol were dissolved in a mixed solvent of 6cc N,N-diethyl lauryl amide and 10cc ethyl acetate while heating at C. The solution was dispersed in 50 cc of 10 percent gelatin containing 2cc of aqueous 5 percent sodium n-dodecylbenzenesulfonate to emulsify. The resulting emulsion was added with 2cc of 2 percent mucochloric acid and with water to make cc. The emulsion was coated on a support of cellulose triacetate so that the dried film thickness was 5,u. A green sensitive iodobromide emulsion layer, which contained 4.8g of gelatin and 3.5 X 10 mols of silver per 100g of emulsion added with either single or the combination of the following sensitizing dyes, was coated thereon so that the dried film thickness was 2p. An emulsion, which was obtained by dissolving 1g of 4-methyl phenyl hydroquinone in a mixed solvent of 2cc N,N-diethyl lauryl amide and 4cc ethyl acetate, emulsifying in 20cc of 10 percent aqueous gelatin solution containing lcc of 5 percent aqueous sodium n-dodecylbenzenesulfonate solution, adding 2cc of 2 percent mucochloric acid and then adding water to make the whole 50cc, was coated thereon so that the dried film thickness might be 08 The film was exposed to light behind an optical wedge having a continuously varied density, impregnated with the alkali reagent of thefollowing compositions:

Hydroxyethyl cellulose of high viscosity 3.5 g NaOH 4.0 g Benzotriazole 2.0 g l-Phenethyl-Z-picolinium bromide 2.0g Water v 100 cc allowed to stand for 2 minutes in contact with the following image-receiving sheet: a gelatin layer containing a mixture of poly-4-vinyl pyridine mordant and 1-phenyl-S-mercaptotetrazole coated on a'Baryta support so that the dried film thickness was lOuand then stripped to yield a positive color developer transfer positive color image, in'which the density of area exposed to a large amount of light was low and that exposed to a small amount of light was high, on the image-receiving sheet. The reflection density of color image obtained on the image-receiving sheet was measured by means of a densitometer to determine the exposure amount at a reflection density of 1.0 and the results are shown in the Tables 1, 2-1, and 2-2. From the Tables, it can be seen that a high green sensitivity is obtained in this invention.

water to make the whole 100cc. The emulsion was coated on a cellulose triacetate support so that the dried film thickness was 4p;

A green sensitive silver iodobromide emulsion layer, which contained 4.8g of gelatin and 3.5 X mols of silver per 100g of emulsion added with either single or the combination of the following sensitizing dyes, was coated thereon so that the dried film thickness was 2o.

An emulsion, which was obtained by dissolving l g of 4-methylphenyl hydroquinone in a mixed solvent-of 2cc N,N-diethyl-lauryl amideand 4cc ethyl acetate, emulsifying in 20cc of 10 percent aqueous gelatin solution containing 5 percent aqueous sodium The concentration of sensitizing dye solution is l X 10"" mel/l.

" The sensitivity is the relative value of the inverse number of the exposure amount required for providing D ll).

Results after the hlack-and-white treatment of the sample, in which a reen sensitive emulsion was coated on a cellulose triacetate. Fuji Filter No. 17 was used as the green ilter.

Table 2 Test No. sensitizing Dye Sensitivitf" (ml/100 g emulsion) 10 l- 6 (2) 70.7 11 do. (4) 100 12 do. (8) 95.5 l3 111-2 (2) 43.7 14 do. (4) 49.6 15 do. (8) 44.5 16 1-6(Z) lll-ZtZ) 107 17 do. (4) do. (2) 174 18 do. (4) do. (4) 174 19 1ll1(2) 63.1 20 do. (4) 100 21 do. (8) 70.7 22 11l-3l2) 50.1 3 do. (4) 56.2 24 do. (8) 52.5 25 1l-1l(2) 111-3 (2) 118 26 do. (4) dov (2) 148 27 do. (4) do. (4) 151 28 l 3 (2) 87.0 29 do. (4) 100. 30 do. (8) 100 31 ll 13(2) 89.0 32 do. (4) 98.0 33 do. (8) 98.0 34 l-3(Z) l1-l3(2) 123 35 do. (4) do. (2) 126 36 dov (4) do. (4) 120 Same as in Table 1. Test No. lU-IS. 19-24 and 28-33 are controls.

EXAMPLE 2 2g of yellow dye developer l-phenyl-3-N-nhexylcarboxyamido-4-(p-(2',5'-dihydroxyphenethyl)- phenylazo)-5,-pyrazolone were dissolved in a mixed solvent of 2cc tricresyl phosphate and Sec cyclohexanone with heating. The solution was emulsified in 50cc of 10 percent gelatin containing 2cc of 5 percent aqueous sodium n-dodecyl benzenesulfonate solution. The emulsion was added with ice of 2 percent aqueous 2- hydroxy-4,6-dichloro-S-triazine solution and then with n-dodecylbenzenesulfonate'solution, adding 200 of 2 percent mucochloric acid and then adding waterto make the whole 50cc, was coated on the layer so that the dried film thickness was 0.8g.

The resulting film was treated in the same manner as in Example 1 to yield a transfer image of dye developer on an image-receiving sheet. The exposure amount at a reflection density of 1.0 is shown in the Table 3, from which it can be seen that a high sensitivity is obtained in this invention.

Table 3 Test No. sensitizing Dye Sensitivity (ml/g emulsion) 37 l 6 (2) 89.0 38 d (4) I00 39 do (8) 95.5 40 Ill-1(2) 52,5 41 C10. (4) S61 42 do. (8) 51.2 43 l-6(2) Ill-1(2) 14] 44 dov (4) do. (Z) 166 45 do. (4) do. (4)

"The sensitivity is indicated in the same manner as in the Table l. The Tests No. 37 42 are controls.

EXAMPLE 3 5g of cyan dye developer 5,8-dihydroxy-1 ,4-bis-[(B- hydroquinonyl-a-methyl )ethylamino anthraquinone were dissolved in a mixed solvent of 10cc N-n butylacetoanilide and 20cc methyl alcohol and the resulting solution was emulsified in 50cc of 10 percent gelatin containing 3cc of 5 percent sodium n-dodecylbenzenesulfonate.

The emulsion was added with 20C of 2 percent aqueous 2-hydroxy-4,6-dichloro-S-triazine solution and then with water to make 100cc. The solution was coated on a cellulose triacetate support so that the dried film thickness was a. A silver iodobromide naphthol were dissolved in 70C of N,N-diethyl lauryl emulsion consisting of 20g of emulsion, which was obamide and 14cc of ethyl acetate with heating and emultained by dissolving 2.0g of 4'-methylphenyl hydroquisified in 100cc of percent gelatin containing 7cc of nine in a mixed solvent of 2cc N-n-butylacetoanilide 5 percent sodium n-dodecylbenzenesulfonate. The and 4cc ethyl acetate and emulsifying in 2000 of 10 5 emulsion was added with 4cc of 2 percent hydroxy-4,6- percent aqueous gelatin solution containing lcc of 5 dichloro-S-triazine and then with water to make the percent aqueous sodium n-dodecylbenzenesulfonate whole 200cc and coated atop the intermediate layer solution, 4.7 X 10 mols of silver per 100g of emulsion (3) so that the dried film thickness was 4.072.

added with either single or the combination of the following sensitizing dyes and 5.3g of gelatin was coated m thereon so that the dried film thickness was 2.5,u. 100cc of 3 percent gelatin containing lcc of 2 percent 2-hydroxy-4,6-dichloro-S-triazine were coated thereon so that the dried film thickness was 0.8 2.

The film was treated in the same manner as in Example l to yield a transfer image of dye developer on an (5) Green Sensitive Emulsion Layer (5 in FIG. 2)

A green sensitive emulsion, in which a silver iodobromide emulsion containing 3.5 X 10" mols per 100g of emulsion and 4.8g'of gelatin added with a single or combination of the following sensitizing dyes, and was coated atop the magentadye developer layer so that the dried film thickness was 3.172.

image-receiving sheet. The exposure amounts at a re- (6) Intermediate Layer (4 in FIG. 2) flection density of 1.0 are shown in Table 4. The same coating as shown in (3) above was coated.

Table 4 Test No. Sensitizing Dye -Sensitivity Green Sensitivity (ml/100 g emulsion) (only green sensitive layer) Without Coupler With Coupler 49 lll-l 2 57.5 74.0 72.0

52 1-4 2 lll-l (2 252 126 I18 53 do. (4 do. (2) 256 135 135 54 do. (4) do. (4) 256 123 126 The sensitivity is indicated in the same manner as in Table l. Tests No. 46 5] are controls.

' Results after the hlack-and-whitc treatment of Sample, in which a green sensitive emulsion was coated on cellulose triacetate. Fuji Filter No. I? was used as green filter. In the Table. the same green sensitive emulsion as in the example was used in only the green sensitive layer without a coupler; for the layer with a coupler. an emulsion was used, in which g/IOO g emulsion of emulsified dispersion prepared by using 10 g of l-hydroxy-N-n-dodecyl-2-naphthamide instead of a cyan dye developer in the preparation of a cyan dye developer emulsion were added to the same green sensitive emulsion.

EXAMPLE 4 atop the green sensitive emulsion layer so that the dried film thickness was 3.5,u. I (7) Yellow Dye Developer Layer (3 in FIG. 2)

5g of l-phenyl-3-N-n-butylcarboxyamido4-(p- The following layers were coated in sequence on a cellulose triacetate support (10 in FIG. 2) to form a multi-layer film. FIG. 2 shows schematically the construction of the thus obtained film. t' 9'" (1) Cyan Developer Layer (9 in FIG 2) were dissolved in a mixed solvent of 5cc N,N- d1ethyl 10g of 1,4 bis (a methyl lg hydmquinonyl lauryl amide and 14cc ethyl acetate and emulsified in ethylamino)-anthra-quinone were dissolved completely 109cc of t percent getatm cohtammg of 5 Percent in a mixed Solvent of 10cc N,N diethy] laurylamide and sodium n-dodecylbenzenesulfonate. The emulsion was 20cc ethyl acetate with heating at 60C for 20 min. The t f Wlth 409 of Percent y y' fi' solution was emulsified in lOOcc of 10 percent gelatin thazme and h water 9 make the whole 2006? containing 10cc of 5 percent sodium n-dodecylbenzene and coated atop the lhtet'medlate layer S that the sulfonate. The emulsion was added with 4cc of 2 perdried film thitflfhess was P" cent 2-hydroxy-4,6-dichloro-S-triaazine and then with (8) Red 'Sehsltlve Emulsloh Layer In FIG Water to make the whole 200cc and Coated so that the A blue sensitive silver iodobromide emulsion condried film thickness was 0 taining 3.6 X [0 mols per 100g of emulsion and 5.3g 2 Red Sensitive Emulsion Layer 8 in FIG. 2 of gelatin was coated atop the yellow y developer A red sensitive silver iodobromide emulsion contain- 55 layer so t the dried l thickness was M- ing 4.7 X 10 mols/100g emulsion and 5.3g of gelatin Protectlve Layer was coated atop the cyan developer layer so that the A q q coatlhg 1h Whlch 100cc. Q the Same a ng dried fil thickness was 52 as shown in (3) above were addedwlth 4cc of 2 percent 3 Intermediate Layer 7 i F1 2 mucochlortc acid, was coated atop the red sensitive 100cc of 5 percent gelatin containing 30g of emulemulSiQh layer 50 a the dried l h S S a 1: sion. which was obtained by dissolving 3g ofphenyl hy- A blue and red light were applied to the whole surdroquinone in a mixed solvent of 3cc N,N-diethyl lauface 'of the resulting film to expose the blue and red ryl amide and 8cc cyclohexane and emulsifying in 30cc sensitive emulsion layer and the film placed behind an of 10 percent gelatin containing 2cc of 5 percent sooptical wedge having a continuously varied density was dium n-dodecylbenzenesulfonate, was coated atop the exposed to green light. The film was dipped in the alkali red sensitive emulsion layer so that the dried film thicktreating reagent described in Example 1, contacted to ness was 4.2,u. the image-receiving sheet described in Example 1 for (4) Magenta Dye Developer Layer (6 in FIG. 2) 2 min. and then separated therefrom to yield'a positive,

7g of 4-ethoxy-2-(p-(B-hydroxyethyl)-phenylazo)-lmagenta dye developer transfer colored imageron the image-receiving sheet, said image having a dye density inversely proportional to the amount of light. The density of said image-receiving sheet was measured todetermine the exposure amount for a density of l.() and the results are shown in Table 5, from which it can be seen that a high sensitivity may be obtained by the process of this invention.

Table 5 Test No. Sensitizing Dye Sensitivity" (ml/100 g emulsion) 55 l l (4) 95 56 do. (8) I 57 lll-l (4) 56 58 do. (8) 63 59 l-l (2) |ll-l (2) 204 60 do. (4) do, (2) 269 6l do.(4) do.(4) 25l "The sensitivity is indicated in the same manner as in Table l. 'l'esls No. 55 58 are controls,

What is claimed is:

1. In a silver photographic emulsion for photographic sensitive material containing dye developers suitable for the diffusion transfer method, the improvement which comprises ,said photographic emulsion, containing a green sensitizer comprising the combination of at least one of the sensitizing dyes represented by the forwherein R is a member selected from the group consisting of a hydrogen atom and lower alkyl group, Y, and Y, each represent a member selected from the group consisting of a hydrogen atom, a lower alkyl group a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acylamido group, an acyloxyl group, a carbalkoxy group and an alkoxycarbonylamino group, Y and Y each represent a member selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, an amino group, an acylamido group, an acyloxy group, a carbalkoxy group, an alkoxycarbonylamino group and a phenyl group, Y and Y,, each represent a member selected from the group consisting of a hydrogen atom and an atomic grouping necesssary for the formation of a benzene ring by the connection of Y,, with Y, or of Y,, with Y Y and Y,-, each can be connected with Y, or Y,, respectively, to form a benzene ring with the proviso that both Y,, with Y, and Y and Y, do not form at the same time a benzene ring and both Y,, with Y,, and Y, with Y, do not form at the same time a benzene ring, R, and R each represent a member selected from the group consisting of an alkyl group and a substituted alkyl group which is used in general for cyanine dyes, and at least one of said R, and said R is an alkyl group containing a member selected from the group consisting of carboxy and sulfo group, X represents an anion and n is l or 2, such that n 1 when said dye forms an intramolecular salt; and at least one of the sensitizing dyes represented by the following formula (ll):

N l t Yii ([1) wherein R,, is a member selected from the group consisting of a lower alkyl group and an ally] group, Y is a member selected from the group con'sistingof a hyd'rogen atom and a halogen atom, Y,, is a member selected from the group consisting of a hydrogen atom,

a halogen atom, an alkoxy group, an amino group, an acylamido group, an acyloxyl group and an alkoxycarbonylamino group, Y,, is a member selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen atom, a hydroxyl group and an alkoxy group, Y,,, is a member selected from the group consisting of a hydrogen atom, a lower alkyl group, a halogen atom, an alkoxy group, a phenyl group, a psulphophenyl group, a carboxyl group, an alkoxycarbonyl group, a cyano group and a trifluoromethyl group, Y,, is a member selected from the group consisting of a hydrogen atom and an atomic grouping which is connected to Y,,, to form a benzene ring, Y,, and Y,,, may be connected to form a benzene ring with the proviso that both Y,,with Y, and Y,,, with Y,, do not form at the same time a benzene ring, and R,, R X and n have the same meanings as in formula (I).

'2. A silver halidephotographic emulsion as claimed in claim I wherein'the substituted alkyl group represented by R, or R is selected from the group consisting ofa hydroxy alkyl group, an acetoxyalkyl group, an alkoxyalkyl group, an alkyl group containing'a carboxyl group; an alkyl group containing a sulfo group, an aralkyl group and an ally] group. r

3. A silver' halide photographic emulsion as claimed in claim '1 wherein the green sensitized combination is selected from combinations comprising sensitizing dyes of omorrrorpom in claim 1 wherein the silver halide is silver iodobromide.

rial comprising an emulsion layer containing a silver halide photographic emulsion as claimed in claim 1. i

8. A light-sensitive silver halide photographic mate-

Claims

1. IN A SILVER PHOTOGRAPHIC EMULSION FOR PHOTOGRAPHIC SENSITIVE MATERIAL CONTAINING DYE DEVELOPERS SUITABLE FOR THE DIFFUSION TRANSFER METHOD, THE IMPROVEMENT WHICH COMPRISES SAID PHOTOGRAPHIC EMULSION CONTAINING A GREEN SENSITIZER COMPRISING THE COMBINATION OF AT LEAST ONE OF THE SENSITIZING DYES REPRESENTED BY THE FORMULA (1):

2. A silver halide photographic emulsion as claimed in claim 1 wherein the substituted alkyl group represented by R1 or R2 is selected from the group consisting of a hydroxy alkyl group, an acetoxyalkyl group, an alkoxyalkyl group, an alkyl group containing a carboxyl group, an alkyl group containing a sulfo group, an aralkyl group and an allyl group.

3. A silver halide photographic emulsion as claimed in claim 1 wherein the green sensitized combination is selected from combinations comprising sensitizing dyes of

4. A silver halide photographic emulsion as claimed in claim 1 wherein the dye developer contains a member selected from the group consisting of hydroquinonyl, o-dihydroxyphenyl and o- or p-amino-substituted hydroxyphenyl.

5. A silver halide photographic emulsion as claimed in claim 1 wherein the dye developer is selected from the group consisting of an azo dye developer and an anthraquinone dye developer.

6. A silver halide photographic emulsion as claimed in claim 5 wherein the dye developer is selected from the group consisting of 4-isopropoxy-2-(p-( Beta -hydroquinonylethyl)-phenylazo)-1-naphthol; 1-phenyl-3-N-n-hexylcarboxyamid-4-(p-(2'',5''-dihydroxyphenethyl)phenylazo)-5 -pyrazolone; and 5,8-dihydroxy-1, 4-bis-(( Beta -hydroquinonyl- Alpha -methyl)-ethylamino)anthraquinone.

7. A silver halide photographic emulsion as claimed in claim 1 wherein the silver halide is silver iodobromide.

8. A light-sensitive silver halide photographic material comprising an emulsion layer containing a silver halide photographic emulsion as claimed in claim 1.